Preparation of alpha-haloalkyl ethers



United States I 1 g 2,888,490 fiiiEPAIiAIION F ALPHA-HALOALKYL ETHERS Ned Foster Walter, Lake Jackson, Rolland Mayden Wa- 1 tars, Frecport, and, John Malcolm Lee, Lake Jackson, .Tex., assignors to The Dow Chemical Company, Midland, Mich., a corporation of Delaware No Drawing. Application July 11, 1957 Serial No. 671,119

4 Claims. (Cl. 260-614) similar reaction using a ketone instead of an aldehyde has not heretofore been successful. In many reactions ketones and aldehydes react similarly due to the ,carbonyl group. However, this reaction is one of the exceptionsto this general similarity in the reactivity of aldehydes and ketones. The alpha-haloalkyl ethers obtained with ketones differ from those obtained with ,aldehydes in that the alpha carbon atom has an alkyl group attached to it instead of a hydrogen. These alphajh'aloalkyl ethers with an alkyl radical attached to the .alpha atom arevery unstable compounds and will readily hydrolyze to an alcohol and ketone. Consequently, at-

tempts to prepare these ethers by the reaction of an alcohoL'ketone, and hydrogen halide have been heretofo're "unsuccessful. They have been prepared by ."clilorination of ketals with phosphorus trichloride. The preparation of ketal is diflicult. Thus, a process where alpha-haloalkyl ethers can be prepared by the reaction 'of a ketone, alcohol, and hydrogen halide is greatly desirable.

It is, therefore, a principal object of this invention to provide a process for the preparation of alpha-halojalkyl ethers of the type having an alkyl radical attached ,to the alpha carbon. A further object is to provide [a process for the preparation of these alpha-haloalkyl .ethers by the reaction of a ketone, alcohol, and a hydrogen halide.

The above and additional objects are accomplished ,byfintermixing an unsubstituted saturated monohydric arcane; having from 1 to 2 carbon atoms, a ketone having a general formula:

were R is a member of the group consisting of alkyl, chloroalkyl, bromoalkyl, and alkoxy radicals having from lto' 2 carbon atoms, and a gaseous hydrogen "halide having a'molecular weight in the range of 36 *to -81 at a temperature in the range of 20 to the frjeezirig point of the resulting mixture. These reactants "are intermixed in proportions such that the molar ratio offthe alcohol to ketorie is in the range of 1:0.8 to

'1':-1.2 and the amount of hydrogen halide is in the range of a stoichiometric proportion to a 500 percent stoichiometric excess. At these low temperatures, the reactants intermixed in the above proportions react to form an alpha-haloalkyl ether.

In a co-pending application No. 579,943, filed April l956 and now Patent Number 2,837,575, by Waters a Lee, co-inventors in the instant application, a process 8 disclosed where ketals may be prepared by reacting atet ether.

"times the reaction mixture. may be recovered from the hydrocarbon phase by flashing off the volatile hydrocarbon under vacuum. Al- 'though the alpha-haloalkyl ether when removed from an alcohol and k'etone in the presence of mineral acids, preferably halogen acids. It has now been discovered that at low temperatures alpha-haloalkyl ethers may be prepared by the reaction of alcohol, ketone, and hydrogen halide. The reaction effected may be illustrated by the following equation showing the reaction of acetone, methanol, and hydrogen chloride:

H O-OH care-ca, omon i101 011 -on, no

Theoretically one mole each of the three reactante is necessary for the reaction. Although it is preferred to use approximately stoichiometric amounts of each of the three reactants, a ratio of alcohol to ketone in the range of 1:0.8 to 1212 may be used. A large excess of alcohol will promote the formation of ketal and thus reduce the yields of the alpha-haloalkyl ether obtained. Likewise, a large excess of ketone is not desirable as it promotes condensation reactions of the ketone. The amount of hydrogen halide used is not as critical as the ratio of alcohol to ketone. It may be increased to about a 500 percent stoichiometric excess without obtaining any appreciable deleterious eifec't.

Aliphatic saturated ketones having three to four carbon atoms may be used. In addition to the unsubstituted ketones, such as acetone and methyl ethyl ketone, halogen substituted and methoxy substituted ketones, such as chloroacetone, methoxyacetone, bromoacetone, and chloromethyl ethyl ketone may also be employed. The alcohols used are the unsubstituted saturated monohydric alcohols having up to 2 carbon atoms, such as methanol and ethanol. With hydrogen chloride or hydrogen bromide, alpha-chloroalkyl ethers or alphabromoalkyl ethers, such as 1,Z-dichloro--2-methoxypropane, 1,2-dibromo-2-methoxypropane, 2-chlo'ro-2-methoxybu'tane, 2-dichloro-2-ethoxypropane, and 2-chloro-1, Z-dimethoxypropane may be prepared. While a reaction temperature as high as 20 C. and as low as a freezing point of the mixture may be used, a temperature in the range of 55 to 65 C. is preferred. Since the reaction in the formation of the alpha-haloalkyl ethers is reversible, small amounts of the alpha-haloalkyl other are obtained at temperatures above -20 C. High temperatures shift the equilibrium favoring the reverse reaction. Due to the reverse reaction, it is preferred to separate the alpha-haloalkyl ether from the reaction mixture at the reaction temperature. The alpha-haloalkyl ether formed may be readily separated from the reactioh mixture by extracting it from the reaction mixture with a volatile saturated hydrocarbon, such as petroleum In contacting the reaction product with a volatile saturated hydrocarbon, the alpha-haloalkyl ether is selectively dissolved in the hydrocarbon forming a hydrocarbon phase which is relatively free of the other constituents of the reaction mixture. Generally, the amount of hydrocarbon solvent used is around 2 to 10 times the volume of the reaction mixture. With a continuous countercurrent extraction process, substantially all of the alpha-haloalkyl ether may be extracted using a volume of the hydrocarbon solvent equal to 2 to 5 times the volume of the reaction product. In a simple single contact extraction process, a larger amount of the solvent is required and the volume used is from 5 to 10 The alpha-haloalkyl ether the reaction mixture may be maintained in the hydro carbon phase at temperatures up to 0 C. for considerable length of time without decomposing, it is preferred to remove the hydrocarbon by flash distillation at a temperature of 10 C. or below.

The rate of reaction of the alcohol, ketone, and hydrogen halide is relatively rapid. Generally in a batch process the alcohol and ketone are intermixed and gaseous hydrogen halide is bubbled into the mixture. The hydrogen halide may be introduced as rapidly as cooling can be effected to maintain the desired low reaction temperature. When a continuous process is used, the ketone and alcohol are charged into a properly cooled tower to which the hydrogen halide is also introduced. The eflluent from reaction tower is immediately passed into an extraction column where the alphahaloalkyl ether is separated from the reaction mixture.

While it is not critical to maintain totally anhydrous conditions, it is preferred to maintain the water concentration in the reaction mixture at a minimum. Water is formed by the reaction and the presence of additional Water only increases the rate of the reverse reaction. Thus to maintain this reverse action at a minimum, the reaction is initiated with relatively water-free reactants.

Example To a three-neck flask equipped with an agitator, a thermometer and a gas delivery tube, 110 ml. (1.5 gm. moles) of acetone and 61 ml. (1.5 gm. moles) of methanol were added. The mixture was cooled to 65 C. Gaseous hydrogen chloride metered through a rotometer was passed into the mixture at a rate such that the mixture could be sufiiciently cooled to maintain the contents of the flask at approximately 65 C. It required about 1% hours to add 1.5 moles of hydrogen chloride.

After the addition of the hydrogen chloride, 20 ml. of the reaction mixture was contacted with 100 ml. of petroleum ether cooled to a temperature of 60" C. to extract the 2-chloro-2methoxypropane from the reaction mixture. Two phases were obtained, a hydrocarbon phase containing the major part of the 2-chloro-2-methoxypropane and a non-hydrocarbon phase containing the other constituents of the reaction mixture. The phases were separated and the non-hydrocarbon phase was again contacted with an additional 100 ml. of petroleum ether. The resulting two phases were again separated and the hydrocarbon phase from the first contact was combined with the hydrocarbon phase obtained in the second contact and analyzed by infrared. It was found to contain 3.13 gm. of Z-chloro-Z-methoxypropane.

The 2chloro-2-methoxypropane is separated from the hydrocarbon solvent by flashing off the hydrocarbon solvent under a vacuum, such as 4 mm. of Hg absolute pressure at which pressure the 2chloro-2-methoxypropane has a boiling point of 12 C.

In the manner similar to that above, hydrogen bromide may be substituted for hydrogen chloride and ethanol for methanol. Also in place of acetone, methyl ethyl ketone, chloroacetone, methoxyacetone, and chloromethyl ethyl ketone may be used.

What is claimed is:

1. A process for the preparation of an alpha-haloalkyl ether by the reaction of an alcohol, ketone, and hydrogen halide, which comprises intermixing an unsubstituted saturated monohydric alcohol having from 1 to 2 carbon atoms, a ketone having the general formula:

CHa-PJ-R where R is a member of the group consisting of alkyl, chloroalkyl, bromoalkyl, and alkoxy radicals having from 1 to 2 carbon atoms, and a gaseous hydrogen halide having molecular weight in the range of 36 to 81 in proportions such that the molar ratio of the alcohol to ketone is in the range of 1:0.8 to 1:12 and the amount of hydrogen halide is in the range of a stoichiometric proportion to a 500 percent stoichiometric excess at a temperature in the range of 20 C. to the freezing point of the resulting mixture thereby to react the alcohol, ketone, and hydrogen halide to form an alpha-haloalkyl ether contacting the resulting mixture with a volatile saturated hydrocarbon at a temperature in the range of 20 C. to the freezing point of the resulting mixture to extract the alphahaloalkyl ether in a hydrocarbon phase from the other constituents of the resulting mixture remaining in a non-hydrocarbon phase, separating the hydrocarbon phase from the non-hydrocarbon phase, and distilling the hydrocarbon phase under vacuum to separate the alpha-haloalkyl ether from. the hydrocarbon phase.

2. A process for preparation of an alpha-haloalkyl ether by the reaction of an alcohol, ketone, and hydrogen halide, which comprises intermixing an unsubstituted saturated monohydric alcohol having from 1 to 2 carbon atoms, a ketone having the general formula:

CH -il-QR where R is a member of the group consisting of alkyl, chloroalkyl, bromoalkyl, and alkoxy radicals having up to 2 carbon atoms, and a gaseous hydrogen halide having a molecular weight in the range of 36 to 81 in equimolar proportions at a temperature in the range of 55 to 65 C. thereby to react the alcohol, ketone, and hydrogen halide to form the alphahaloalkyl ether, contacting the resulting mixture with a volatile saturated hydrocarbon in a proportion of from 2 to 10 times the volume of resulting mixture at the reaction temperature to extract the alpha-haloalkyl ether in a hydrocarbon phase from the other constituents remaining in a non-hydrocarbon phase, separating the hydrocarbon phase from the non-hydrocarbon phase, and distilling the hydrocarbon phase under vacuum at a temperature below 10 C. to separate the alpha-haloalkyl ether from the hydrocarbon phase.

3. A process for the preparation of 2-chloro-2-ethoxypropane which comprises intermixing ethanol, acetone, and gaseous hydrogen chloride in equimolar proportions at a temperature in the range of 55 to 65 C. thereby to react the ethanol, acetone, and hydrogen chloride to form the 2chloro-Z-ethoxypropane, contacting the re sulting mixture with a volatile saturated hydrocarbon in a proportion of from 2 to 10 times the volume of resulting mixture at the reaction temperature to extract the alphahaloalkyl ether in a hydrocarbon phase from the other constituents remaining in a non-hydrocarbon phase, separating the hydrocarbon phase from the non-hydrocarbon phase, and distilling the hydrocarbon phase under vacuum at a temperature below -l0 C. to separate the alpha-haloalkyl ether from the hydrocarbon phase.

4. A process for preparation of 2-chloro-2-methoxypropane, which comprises intermixing methanol, acetone, and gaseous hydrogen chloride in equimolar proportions at a temperature in the range of 55 to 65 C. thereby to react the methanol, acetone, and hydrogen chloride to form the 2chloro-Z-methoxypropane, contacting theresulting mixture with a volatile saturated hydrocarbon in proportions of from 2 to 10 times the volume of the resulting mixture at a temperature in the range of 55 to -65 C. to extract the 2-chloro-2-methoxypropane formed in a hydrocarbon phase from the other constituents of the resulting mixture remaining in a non-hydrocarbon phase, separating the hydrocarbon phase from the non-hydrocarbon phase, and distilling the hydrocarbon phase under vacuum to separate the Z-chloro-Z-methoxypropane from the hydrocarbon phase. 

1. A PROCESS FOR THE PREPARATION OF AN ALPHA-HALOALKYL ETHER BY THE REACTION OF AN ALCOHOL, KETONE, AND HYDROGEN HALIDE, WHICH COMPRISES INTERMIXING AN UNSUBSTITUTED SATURATED, MONOHYDRIC ALCOHOL HAVING FROM 1 TO 2 CARBON ATOMS, A KETONE HAVING THE GENERAL FORMULA: 